ChemInform Abstract: CYCLISIERUNG VON CYCLOHEXANDIOL‐(1,2)‐MONO‐(ALPHA,ALPHA‐DIMETHYL‐PROPARGYLAETHER) UNTER HYDRATISIERUNGSBEDINGUNGEN

Karaev, S. F.; Movsumzade, M. M.; Askerov, M. E.

doi:10.1002/chin.197514268

Chemischer Informationsdienst

1975

DOI: 10.1002/chin.197514268

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ChemInform Abstract: CYCLISIERUNG VON CYCLOHEXANDIOL‐(1,2)‐MONO‐(ALPHA,ALPHA‐DIMETHYL‐PROPARGYLAETHER) UNTER HYDRATISIERUNGSBEDINGUNGEN

S. F. Karaev¹,

M. M. Movsumzade²,

M. E. Askerov³

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“…This reaction opens a simple route to previously unknown but undoubtedly promising cyclic polyether acetals possessing highly reactive 2-propynyloxy groups in the side chain. Karaev et al [28] previously desribed an example of acid-catalyzed cyclization of 2-(1,1-dimethyl-2-propynyloxy)cyclohexanol with participation of the hydroxy group and the triple bond under hydration conditions (H 2 O, HgO-H 2 SO 4 , 50-60°C, 2 h); the product of this reaction was 2,3,3-trimethyloctahydro-1,4-benzodioxin-2-ol (yield 50%).…”

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Vinyl Ethers Containing an Epoxy Group: XXII. Synthesis and Base-Catalyzed Transformations of 1-(Allyloxy)- and 1-[2-(Vinyloxy)ethoxy]-3-(2-propynyloxy)propan-2-ols

et al. 2005

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Reactions of 2-(allyloxymethyl)-and 2-[2-(vinyloxy)ethoxy]methyloxiranes with 2-propynol (~3 wt % of t-BuOK, 75-85°C, 5-10 h) lead to formation of new 1-organyloxy-3-(2-propynyloxy)propan-2-ols (yield 65-95%). On heating to 45-100°C in the presence of bases (KOH, t-BuOK), 1-allyloxy-and 1-[2-(vinyloxy)ethoxy]-3-(2-propynyloxy)propan-2-ols are transformed into the corresponding 2-vinyl-1,3-dioxolane, 6-methyl-2,3-dihydro-1,4-dioxine, 6-methylene-1,4-dioxane, and 2,3-dihydro-5H-1,4-dioxepine derivatives, whose yield and ratio strongly depend on the solvent nature, catalyst, and substituent at the hydroxy group. 2-Vinyl-1,3-dioxolane and 6-methyl-2,3-dihydro-1,4-dioxine derivatives are formed as the major products (yield 70-99%) in the presence of t-BuOK in aprotic media (toluene, THF, DMSO) or in the absence of a solvent as a result of prototropic isomerization followed by intramolecular heterocyclization. Intramolecular nucleophilic cyclization of 3-(2-propynyloxy)propan-2-ols to 6-methylene-1,4-dioxane is the predominant process in water in the presence of KOH. In all cases, the fraction of 2,3-dihydro-5H-1,4-dioxepine derivatives among the cyclization products ranges from 0 to 5% (KOH) or to 14% (t-BuOK). * For communication XXI, see [1]. Base-catalyzed intramolecular cyclizations of -(2-propynyloxy)-[2-8], -(2-propynylsulfanyl)-[9], and -(2-propynylamino)alkan-1-ols [10,11], as well as of their 2-haloallyl analogs [4,5,9], have been studied in sufficient detail. Such cyclizations (which involve intramolecular nucleophilic addition of functional group at the acetylenic triple bond) are among the most widespread reactions leading to five-, six-, or seven-membered heterocycles containing one or two heteroatoms (N, O, S) [8,12, 13]. However, in the series of -(2-propynyloxy)alkan-1-ols, only 2-(2-propynyloxy)ethanol and its simplest derivatives R 1 C CC(R 2 )(R 3 )OCH(R 4 )CH(R 5 )OH (R 1 = R 2 = R 3 = R 4 = R 5 = H [3, 4, 7]; R 1 = R 2 = R 3 = R 4 = H, R 5 = Me, Ph; R 1 = R 2 = R 3 = R 5 = H, R 4 = Ph; R 1 = R 2 = R 3 = H, R 4 = R 5 = Me [3, 6]; R 1 = R 2 = R 4 = R 5 = H, R 3 = Me [7]; R 1 = R 4 = R 5 = H, R 2 = Me, R 3 = Ph [8]; R 1 = R 2 = R 4 = H, R 3 = R 5 = Me [3, 6, 7]; R 1 = Me, R 2 = R 3 = R 4 = R 5 = H [7]), 3-(2-propynyloxy)propan-1-ol [5], 2-(2-propynyloxy)cyclopentanol [7], and 2-(2-propynyloxy)cyclohexanol [3, 6, 7] were studied.Obviously, introduction of additional reaction centers, e.g., olefinic fragments with qualitatively different chemical natures of the double carbon-carbon bonds (specifically vinyloxy and allyloxy groups), into (2-propynyloxy)alkanol molecules should strongly extend the synthetic potential of both initial alkanols [1][2][3][4][5][6][7][8]12] and their cyclization products [1,8,14], as well as the range of their useful properties and the scope of practical application. Known representatives of this class of compounds are used in various fields (see, e.g., references in [1]), including the synthesis of dendrimers, dienes, -hydroxy and -oxo acids, -hydroxymethyl ketones, , '-dihy...

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Vinyl Ethers Containing an Epoxy Group: XXII. Synthesis and Base-Catalyzed Transformations of 1-(Allyloxy)- and 1-[2-(Vinyloxy)ethoxy]-3-(2-propynyloxy)propan-2-ols

et al. 2005

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ChemInform Abstract: CYCLISIERUNG VON CYCLOHEXANDIOL‐(1,2)‐MONO‐(ALPHA,ALPHA‐DIMETHYL‐PROPARGYLAETHER) UNTER HYDRATISIERUNGSBEDINGUNGEN

Cited by 1 publication

References 0 publications

Vinyl Ethers Containing an Epoxy Group: XXII. Synthesis and Base-Catalyzed Transformations of 1-(Allyloxy)- and 1-[2-(Vinyloxy)ethoxy]-3-(2-propynyloxy)propan-2-ols

Vinyl Ethers Containing an Epoxy Group: XXII. Synthesis and Base-Catalyzed Transformations of 1-(Allyloxy)- and 1-[2-(Vinyloxy)ethoxy]-3-(2-propynyloxy)propan-2-ols

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